Fermi level pinning induced electrostatic fields and band bending at organic heterojunctions

The energy level alignment at interfaces between organic semiconductors is of direct relevance to understand charge carrier generation and recombination in organic electronic devices. Commonly, work function changes observed upon interface formation are interpreted as interface dipoles. In this study, using ultraviolet and X ray photoelectron spectroscopy, complemented by electrostatic calculations, we find a huge work function decrease of up to 1.4 amp; 8201;eV at the C60 bottom layer zinc phthalocyanine ZnPc, top layer interface prepared on a molybdenum trioxide MoO3 substrate. However, detailed measurements of the energy level shifts and electrostatic calculations reveal that no interface dipole occurs. Instead, upon ZnPc deposition, a linear electrostatic potential gradient is generated across the C60 layer due to Fermi level pinning of ZnPc on the high work function C60 MoO3 substrate, and associated band bending within the ZnPc layer. This finding is generally of importance for understanding organic heterojunctions when Fermi level pinning is involved, as induced electrostatic fields alter the energy level alignment significantl

Organic semiconductor density of states controls the energy level alignment at electrode interfaces

Minimizing charge carrier injection barriers and extraction losses at interfaces between organic semiconductors and metallic electrodes is critical for optimizing the performance of organic opto electronic devices. Here, we implement a detailed electrostatic model, capable of reproducing the alignment between the electrode Fermi energy and the transport states in the organic semiconductor both qualitatively and quantitatively. Covering the full phenomenological range of interfacial energy level alignment regimes within a single, consistent framework and continuously connecting the limiting cases described by previously proposed models allows us to resolve conflicting views in the literature. Our results highlight the density of states in the organic semiconductor as a key factor. Its shape and, in particular, the energy distribution of electronic states tailing into the fundamental gap is found to determine both the minimum value of practically achievable injection barriers as well as their spatial profile, ranging from abrupt interface dipoles to extended band bending region

Electronic properties and degradation upon VUV irradiation of sodium chloride on Ag 111 studied by photoelectron spectroscopy

The growth as well as vacuum ultraviolet VUV radiation induced degradation of sodium chloride NaCl on Ag 111 is investigated by ultraviolet and x ray photoelectron spectroscopy. In line with previous scanning tunneling microscopy studies, our results confirm that NaCl grows initially as a bilayer before island growth starts. Simple spectroscopic methods for calibrating the closure of the NaCl bilayer are further presented. In addition, the energy level alignment is studied as a function of NaCl film thickness and VUV light intensity. When measuring with ultra low photon flux, a sharp interface dipole lowers the sample work function by 0.65 eV upon adsorption of the first bilayer, which is followed by vacuum level alignment for subsequently deposited layers. In contrast, measurements performed with standard photon fluxes, such as those provided by commercial He discharge lamps, shows downward band bending like characteristics in the NaCl films. Upon extended exposure time to the standard VUV intensity, photoemission measurements further reveal that strong modifications of the electronic properties of the NaCl surface occur. These are likely correlated with halogen emission, eventually resulting in the formation of Na clusters promoting low work function of parts of the sample surface. This study provides general guidelines for obtaining reliable spectroscopic measurements on alkali halide thin films on metal

Charge transfer crystallites as molecular electrical dopants

Ground-state integer charge transfer is commonly regarded as the basic mechanism of molecular electrical doping in both, conjugated polymers and oligomers. Here, we demonstrate that fundamentally different processes can occur in the two types of organic semiconductors instead. Using complementary experimental techniques supported by theory, we contrast a polythiophene, where molecular p-doping leads to integer charge transfer reportedly localized to one quaterthiophene backbone segment, to the quaterthiophene oligomer itself. Despite a comparable relative increase in conductivity, we observe only partial charge transfer for the latter. In contrast to the parent polymer, pronounced intermolecular frontier-orbital hybridization of oligomer and dopant in 1:1 mixed-stack co-crystallites leads to the emergence of empty electronic states within the energy gap of the surrounding quaterthiophene matrix. It is their Fermi–Dirac occupation that yields mobile charge carriers and, therefore, the co-crystallites—rather than individual acceptor molecules—should be regarded as the dopants in such systems

High sensitivity organic inorganic hybrid X-ray detectors with direct transduction and broadband response

X-ray detectors are critical to healthcare diagnostics, cancer therapy and homeland security, with many potential uses limited by system cost and/or detector dimensions. Current X-ray detector sensitivities are limited by the bulk X-ray attenuation of the materials and consequently necessitate thick crystals (~1 mm-1 cm), resulting in rigid structures, high operational voltages and high cost. Here we present a disruptive, flexible, low cost, broadband, and high sensitivity direct X-ray transduction technology produced by embedding high atomic number bismuth oxide nanoparticles in an organic bulk heterojunction. These hybrid detectors demonstrate sensitivities of 1712 µC mGy-1 cm-3 for "soft" X-rays and ~30 and 58 µC mGy-1 cm-3 under 6 and 15 MV "hard" X-rays generated from a medical linear accelerator; strongly competing with the current solid state detectors, all achieved at low bias voltages (-10 V) and low power, enabling detector operation powered by coin cell batteries

The Impact of Disorder on the Energy Level Alignment at Molecular Donor Acceptor Interfaces

Introductory paragraph Organic photovoltaic cells OPVCs have attracted considerable interest in the last three decades, because of their advantages over conventional inorganic photovoltaics in terms of easy processability roll to roll , low cost of production, and the possibility of fabricating ultra thin and fl exible devices. [ 1 ] At the heart of modern OPVCs is a type II heterojunction that splits photogenerated electron hole pairs and transports the resulting mobile charge carriers to their respective contacts. [ 2 ] This interface, consisting of electron donor and acceptor type molecular semiconductors, is therefore key to the photocurrent generation in an OPVC. [ 3 ] By optimizing the optical bandgaps of the organic semiconductors and the positions of the electronic levels with respect to each other, power conversion effi ciencies of 10 can be reached, even for single junction OPVCs. [ 4 ] Therefore, precisely knowing the offsets between the solidstate values for the energies of the highest occupied molecular orbitals HOMO and the lowest unoccupied molecular orbitals LUMO is essential for effi cient devices. In addition, a thorough understanding of the electronic processes occurring at these donor acceptor interfaces is crucial to establish rational design principles of, e.g., interface morphology and, ultimately, to improve future organic materials. [ 5